CN108117668A - The fire retardant of one kind structure containing melamine, preparation method and applications - Google Patents
The fire retardant of one kind structure containing melamine, preparation method and applications Download PDFInfo
- Publication number
- CN108117668A CN108117668A CN201810035973.7A CN201810035973A CN108117668A CN 108117668 A CN108117668 A CN 108117668A CN 201810035973 A CN201810035973 A CN 201810035973A CN 108117668 A CN108117668 A CN 108117668A
- Authority
- CN
- China
- Prior art keywords
- compound
- fire retardant
- melamine
- retardant
- containing melamine
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 40
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000004699 copper complex Chemical class 0.000 claims abstract description 16
- -1 methoxyl group Chemical group 0.000 claims abstract description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004440 column chromatography Methods 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000013177 MIL-101 Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001514 detection method Methods 0.000 claims description 11
- 229940125904 compound 1 Drugs 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 229940125782 compound 2 Drugs 0.000 claims description 5
- 229940126214 compound 3 Drugs 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000002153 concerted effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 235000019441 ethanol Nutrition 0.000 description 11
- FAGLEPBREOXSAC-UHFFFAOYSA-N tert-butyl isocyanide Chemical compound CC(C)(C)[N+]#[C-] FAGLEPBREOXSAC-UHFFFAOYSA-N 0.000 description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 0 CC(N)N=C(N)N=C(*)N Chemical compound CC(N)N=C(N)N=C(*)N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- PKHLXUFAZRWDCB-UHFFFAOYSA-N 4-n-methyl-2-(4-methylpiperazin-1-yl)-5-nitropyrimidine-4,6-diamine Chemical compound NC1=C([N+]([O-])=O)C(NC)=NC(N2CCN(C)CC2)=N1 PKHLXUFAZRWDCB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LAFKQEGCOQBGHH-XFFZJAGNSA-N CCC(C/C=C(\N(CC(NC(C)(C)C)=O)C=O)/N=C(N)N)C(N)=[IH] Chemical compound CCC(C/C=C(\N(CC(NC(C)(C)C)=O)C=O)/N=C(N)N)C(N)=[IH] LAFKQEGCOQBGHH-XFFZJAGNSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000006058 Ugi-reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention relates to the fire retardant of one kind structure containing melamine, preparation method and applications, chemical structural formula is：Wherein, substituent R1、R2And R3For any one in hydrogen, tertiary butyl, normal-butyl, cyclohexylalkyl or chloride, bromine, methyl, methoxyl group, nitro, amino, hydroxyl substituted aryl or heteroaryl.Synthetic method is that the Ugi occurred under the concerted catalysis of the copper complex, MIL 101 and the p-methyl benzenesulfonic acid that are loaded with carboxylic acid compound and melamine, aldehyde compound and different nitrile compounds in MCM 41 at 50 DEG C in the in the mixed solvent of methanol and isopropanol reacts, and product must contain the fire retardant of melamine by filtering, extraction and column chromatography.The invention describes that a kind of reaction is simple, by-product is few, the preferable novel preparation method of selectivity is used for selectively production of melamine based flame retardant.The fire retardant thermostabilization of the present invention is good, and fire-retardant rate is high, and up to 97.2%, used raw material is easy to get purity, technique is advanced, is easy to industrialized production.
Description
Technical field
The present invention relates to the fire retardant of one kind structure containing melamine, preparation method and applications researchs.
Background technology
There are secondary hazards such as thickness, the releasings of toxic or corrosive gas when traditional halogen fire proofing burns, to people
Body constitutes safely serious threat, therefore finds new halogen-free flame retardants and be particularly important.Melamine based flame retardant because
With Halogen low toxicity；Decomposition temperature is high, is suitble to processing；Mechanical performance is influenced small；It does not ooze out, does not corrode mold；Flame retardant property
The characteristics such as excellent, the new and effective fire retardant of the structure containing melamine have very big Development volue, cause people widely studied.
In Britain, the ground such as Europe and North America, melamine analog derivative be used to improve polyurethane foamed plastics flame retardant property, and oneself expands
It opens up in other kinds of polymer, such as hard poly- cruel foamed plastics of ammonia, thermoplastic.The application test model of nearest melamine
It encloses and is expanded to nylon and the fields such as pvc pipe.Melamine can be as the reason for excellent flame retardant three when 250~450
Poly cyanamid absorbs heat, reaction of decomposing, and releases ammonia, forms condensation polymer；The melting behavior of basis material is influenced, and accelerates its charcoal
Chemical conversion is burnt.But the fire retardant of the structure containing melamine is applied at present and development is relatively slow, has put into the product commercially produced
It is few, low yield, price high the shortcomings of complicated there are synthesis technology.
Patent of the present invention introduces three kinds of copper complex of MCM-41 loads, MIL-101 and p-methyl benzenesulfonic acid catalyst, passes through
The mechanism of three kinds of catalyst concerted catalysis, catalysis carboxylic acid compound and melamine, aldehyde compound and isonitrile class chemical combination
The Ugi reactions that four component of object participates in, one pot of colleges and universities are prepared for the fire retardant of the structure containing melamine of a series of new.
The content of the invention
It is a primary object of the present invention to provide the fire retardant of a kind of structure containing melamine, preparation method and applications are ground
Study carefully.
Technical scheme is as follows：
The fire retardant of one kind structure containing melamine, the compound chemical structure formula are：
Wherein, substituent R1、R2And R3For the alkyl such as hydrogen, tertiary butyl, normal-butyl, cyclohexyl or chloride, bromine, methyl, methoxy
Any one in the substituted aryls such as base, nitro, amino, hydroxyl or heteroaryl, substituting group position, number and conjugate position are not
It is fixed.
Further preferably described reaction equation is：
Further preferably described reaction equation is：
Further preferably described reaction equation is：
The synthesis method, the described method includes following synthesis paths：
It the described method comprises the following steps：
(1) under nitrogen protection, compound 1, compound 2, compound 3, compound 4, first are sequentially added into reactor
The mixed solvent of alcohol and isopropanol, being stirred 30 minutes at 45-60 DEG C makes its dissolving；
(2) copper complex, MIL-101 and the p-methyl benzenesulfonic acid that catalyst MCM-41 loads are sequentially added after dissolving continue to stir
It mixes, while temperature is reduced to 20-40 DEG C, the reaction was continued 20-28h after the completion of TLC detection reactions, removes solvent methanol under reduced pressure
And ethyl alcohol, residue is filtered, extraction and column chromatography, obtains target compound I, completes the preparation of melamine based flame retardant.
Compound 1 in the step (1), compound 2, compound 3, the molar ratio of compound 4 is 2-5：0.1-2：1-4： 1-4.
Further preferably middle compound 1, compound 2, compound 3, the molar ratio of compound 4 is 3.3：1：3： 3.15.
Compound 1 in the step (1), copper complex, MIL-101 and the p-methyl benzenesulfonic acid that catalyst MCM-41 is loaded
The mass ratio that feeds intake is 1：0.05-1：0.05-1：0.05-1.
The solution temperature of the step (1) is 50 DEG C；The reaction temperature of step (2) is 40 DEG C.
Step (1) solvent is methanol and the mixed solvent of isopropanol, and the volume ratio of methanol and isopropanol is 2：1.
Catalyst described in the step (2) is the copper complex of MCM-41 loads, MIL-101 and p-methyl benzenesulfonic acid
Mixed catalyst.
The fire retardant of the structure containing melamine described in any one adds in epoxy resin, polyurethane cooperative flame retardant
Add the application in agent.
The present invention has the beneficial effect that：
1st, present invention firstly discloses three kinds of the copper complexes, MIL-101 and p-methyl benzenesulfonic acid loaded with a kind of MCM-41
The strategy that catalyst collaboration is urged prepares a series of syntheti c route of melamine based flame retardants.This method is easy to operate, by-product
It is few, there is higher use value.
2nd, the present invention is prepared for the fire retardant of a new class of structure containing melamine, provides that a kind of manufacturing cost is low, behaviour
Make simple and high reaction efficiency novel preparation method.
3rd, the present invention is prepared for the fire retardant of a new class of structure containing melamine, which has thermostabilization
Well, the advantages that fire-retardant rate is high.The new flame retardant is the important supplement of melamine based flame retardant, at the same epoxy resin,
There are higher potentiality and wide application value on polyurethane cooperative flame retardant additive.
Specific embodiment
It is further illustrated the present invention with reference to embodiment, but the scope of protection of present invention is not limited to implement
The scope of example statement.
Instrument and reagent：
SHZ-E type circulating water types vacuum pump (the biochemical instrument plants of Shanghai Rong Ya)；DZE-6120 type vacuum drying chambers (Shanghai
Heng Tian scientific instrument manufacturing company)；WRS-1A numeral melting point instruments (Shanghai Suoguang Optoelectronic Technology Co., Ltd.)；EB2005A electronics
Balance；ZF-I type ultraviolet analysis instrument for three purposed；DE-102J heat collecting types constant-temperature heating magnetic stirring apparatus (Gongyi City's grey hair chemical apparatuses
Factory)；DFX-5L/30 cryogenic thermostats reactive bath technique (hundred river instrument plant of Wuxi City)；(Linhai City is forever for 2YZ-4A type rotary vane types vacuum oil pump
Vast and boundless vacuum equipment factory).Formic acid (AR), p-methyl benzenesulfonic acid (AR), formaldehyde (AR), tert-butyl isonitrile (AR), acetic acid (AR), benzoic acid
(AR), methanol (AR), isopropanol (AR), ethyl acetate (AR), industrial nitrogen (AR).
Specific embodiment
It is further illustrated the present invention with reference to embodiment, but the scope of protection of present invention is not limited to implement
The scope of example statement.
Instrument and reagent：
Fusing point is measured with X4 types melting point apparatus (production of the 3rd optical instrument factory of Beijing), and thermometer is not calibrated；1H NMR and13C NMR 600 type 600MHz cores of 400 type 400MHz Nuclear Magnetic Resonance of Varian Mercury or Varian Mercury
Magnetic resonance device measures, deuterochloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO-d6) it is solvent, TMS is internal standard；MS is used
FinniganTrace mass spectrographs measure；Elemental analysis is measured using Vario EL III elemental analysers；Agents useful for same is domestic
(or import) chemistry is pure or analysis is pure.Solvent methanol and isopropanol are dried.
Embodiment 1
It is a kind of to prepare N- (tert-butyl) -2- (N- (4,6-diamino-1,3,5-triazin-2-yl)
Formamido) the method for acetamide fire retardants, including following experimental procedure：
Under nitrogen protection, compound melamine 1 (0.378g, 3mmol, 3.0eqv.), first are sequentially added into reactor
Sour 2a (0.046g, 1.0mmol, 1.0eqv.), formaldehyde 3a (0.030g, 1.0mmol, 1.0eqv.), tert-butyl isonitrile 4a
(0.091g, 1.1mmol, 1.1eqv.), MeOH:I-PrOH=2:1 (10ml), being heated to 50 DEG C of stirrings makes its molten in 30 minutes
Solution.Copper complex (0.025g), the MIL-101 (0.025g) and to toluene sulphur of catalyst MCM-41 loads are sequentially added after dissolving
Sour (0.017g) continues to stir, while temperature is reduced to 40 DEG C, after the reaction was continued for 24 hours, after the completion of TLC detection reactions, under reduced pressure
Solvent methanol and ethyl alcohol are removed, residue is filtered, extraction and column chromatography, obtains target fire retardant Ia, yield 57.01%.
Yield：57.01%
Elemental analysis：45.31 H% of measured value C%, 6.02 N% 37.79
44.94 H% of calculated value C%, 6.41 N% 36.68
1H NMR(CDCl3,400MHz)δ(ppm)8.31-8.03(s,1H,CO-H),7.13-5.19(m,6H,CH,NH,
2NH2),1.51-1.13(s,9H,3CH3).
HRMS Calculatedfor[C10H17N7O2+H]+:268.1522,Found:268.1461.
Embodiment 2
It is a kind of to prepare octyl 2- (2- (N- (4,6-diamino-1,3,5-triazin-2-yl) formamido)
Acetamido) the method for acetate fire retardants, including following experimental procedure：
Under nitrogen protection, compound melamine 1 (0.378g, 3mmol, 3.0eqv.), first are sequentially added into reactor
Sour 2a (0.046g, 1.0mmol, 1.0eqv.), formaldehyde 3a (0.030g, 1.0mmol, 1.0eqv.), acetic acid n-octyl isonitrile 4b
(0.22 g, 1.1mmol, 1.1eqv.), MeOH:I-PrOH=2:1 (10ml), being heated to 50 DEG C of stirrings makes its dissolving in 30 minutes.
Copper complex (0.025g), MIL-101 (0.025g) and the p-methyl benzenesulfonic acid of catalyst MCM-41 loads are sequentially added after dissolving
(0.017g) continues to stir, while temperature is reduced to 40 DEG C, after the reaction was continued for 24 hours, after the completion of TLC detection reactions, removes under reduced pressure
Remove solvent methanol and ethyl alcohol, residue is filtered, extraction and column chromatography, obtains target fire retardant Ia, yield 41.30%.
Yield：41.30%
Embodiment 3
It is a kind of to prepare octyl 2- (2- (N- (4,6-diamino-1,3,5-triazin-2-yl) -4-
Nitrobenzamido) acetamido) acetate fire retardants method, including following experimental procedure：
Under nitrogen protection, compound melamine 1 (0.378g, 3mmol, 3.0eqv.) is sequentially added into reactor, it is right
Nitrobenzoic acid 2b (0.167g, 1.0mmol, 1.0eqv.), formaldehyde 3a (0.030g, 1.0mmol, 1.0eqv.), acetic acid is just pungent
Ester isonitrile 4b (0.22g, 1.1mmol, 1.1eqv.), MeOH:I-PrOH=2:1 (10ml), be heated to 50 DEG C of stirrings makes for 30 minutes
It is dissolved.Copper complex (0.025g), the MIL-101 (0.025g) and to first of catalyst MCM-41 loads are sequentially added after dissolving
Benzene sulfonic acid (0.017g) continues to stir, while temperature is reduced to 40 DEG C, after the reaction was continued for 24 hours, after the completion of TLC detection reactions, is subtracting
Pressure removes solvent methanol and ethyl alcohol, and residue is filtered, extraction and column chromatography, obtains target fire retardant Ia, yield
33.97%.
Yield：33.97%
Embodiment 4
It is a kind of to prepare N- (tert-butyl) -2- (N- (4,6-diamino-1,3,5-triazin-2-yl)
Formamido) the method for acetamide fire retardants, including following experimental procedure：
Under nitrogen protection, compound melamine 1 (0.378g, 3mmol, 3.0eqv.), first are sequentially added into reactor
Sour 2a (0.046g, 1.0mmol, 1.0eqv.), formaldehyde 3a (0.030g, 1.0mmol, 1.0eqv.), tert-butyl isonitrile 4a
(0.091g, 1.1mmol, 1.1eqv.), MeOH:I-PrOH=2:1 (10ml), being heated to 50 DEG C of stirrings makes its dissolving in 30 minutes.
Copper complex (0.050g), MIL-101 (0.050g) and the p-methyl benzenesulfonic acid of catalyst MCM-41 loads are sequentially added after dissolving
(0.034g) continues to stir, while temperature is reduced to 40 DEG C, after the reaction was continued for 24 hours, after the completion of TLC detection reactions, removes under reduced pressure
Remove solvent methanol and ethyl alcohol, residue is filtered, extraction and column chromatography, obtains target fire retardant Ia, yield 51.36%.
Embodiment 5
It is a kind of to prepare N- (tert-butyl) -2- (N- (4,6-diamino-1,3,5-triazin-2-yl)
Formamido) the method for acetamide fire retardants, including following experimental procedure：
Under nitrogen protection, compound melamine 1 (0.378g, 3mmol, 3.0eqv.), first are sequentially added into reactor
Sour 2a (0.046g, 1.0mmol, 1.0eqv.), formaldehyde 3a (0.030g, 1.0mmol, 1.0eqv.), tert-butyl isonitrile 4a
(0.091g, 1.1mmol, 1.1eqv.), MeOH:I-PrOH=2:1 (10ml), being heated to 50 DEG C of stirrings makes its molten in 30 minutes
Solution.Copper complex (0.0125g), the MIL-101 (0.0125g) and to toluene of catalyst MCM-41 loads are sequentially added after dissolving
Sulfonic acid (0.008g) continues to stir, while temperature is reduced to 40 DEG C, after the reaction was continued for 24 hours, after the completion of TLC detection reactions, is depressurizing
Lower removing solvent methanol and ethyl alcohol, residue is filtered, extraction and column chromatography, obtains target fire retardant Ia, yield 49.53%.
Embodiment 6
Under nitrogen protection, compound melamine 1 (3.78g), formic acid 2a (0.46g), first are sequentially added into reactor
Aldehyde 3a (0.30g), tert-butyl isonitrile 4a (0.91g), MeOH:I-PrOH=2:1 (100ml) is heated to 50 DEG C and stirs 30 minutes
Make its dissolving.Copper complex (0.25g), the MIL-101 (0.25g) and to first of catalyst MCM-41 loads are sequentially added after dissolving
Benzene sulfonic acid (0.17g) continues to stir, while temperature is reduced to 40 DEG C, after the reaction was continued for 24 hours, after the completion of TLC detection reactions, is depressurizing
Lower removing solvent methanol and ethyl alcohol, residue is filtered, extraction and column chromatography, obtains target fire retardant Ia, yield 49.70%.
Yield：49.70%.
Embodiment 7
Under nitrogen protection, compound melamine 1 (0.0378g), formic acid 2a are sequentially added into reactor
(0.0046g), formaldehyde 3a (0.0030g), tert-butyl isonitrile 4a (0.0091g), MeOH:I-PrOH=2:1 (1ml), is heated to
50 DEG C of stirrings make its dissolving in 30 minutes.Sequentially added after dissolving catalyst MCM-41 load copper complex (0.0025g),
MIL-101 (0.0025 g) and p-methyl benzenesulfonic acid (0.0017g) continue to stir, while temperature is reduced to 40 DEG C, and the reaction was continued for 24 hours
Afterwards, after the completion of TLC detections reaction, solvent methanol and ethyl alcohol are removed under reduced pressure, and residue is filtered, extraction and column chromatography, obtains
To target fire retardant Ia, yield 52.58%.
Yield：52.58%.
Embodiment 8
Under nitrogen protection, compound melamine 1 (0.378g, 3mmol, 3.0eqv.), first are sequentially added into reactor
Sour 2a (0.046g, 1.0mmol, 1.0eqv.), formaldehyde 3a (0.030g, 1.0mmol, 1.0eqv.), tert-butyl isonitrile 4a
(0.091g, 1.1mmol, 1.1eqv.), MeOH:I-PrOH=2:1 (5ml), being heated to 50 DEG C of stirrings makes its dissolving in 30 minutes.
Copper complex (0.025g), MIL-101 (0.025g) and the p-methyl benzenesulfonic acid of catalyst MCM-41 loads are sequentially added after dissolving
(0.017g) continues to stir, while temperature is reduced to 40 DEG C, after the reaction was continued for 24 hours, after the completion of TLC detection reactions, removes under reduced pressure
Remove solvent methanol and ethyl alcohol, residue is filtered, extraction and column chromatography, obtains target fire retardant Ia, yield 53.29%.
Yield：53.29%.
Embodiment 9
Under nitrogen protection, compound melamine 1 (0.378g, 3mmol, 3.0eqv.), first are sequentially added into reactor
Sour 2a (0.046g, 1.0mmol, 1.0eqv.), formaldehyde 3a (0.030g, 1.0mmol, 1.0eqv.), tert-butyl isonitrile 4a
(0.091g, 1.1mmol, 1.1eqv.), MeOH:I-PrOH=2:1 (10ml), being heated to 50 DEG C of stirrings makes its molten in 30 minutes
Solution.Copper complex (0.025g), the MIL-101 (0.025g) and to toluene sulphur of catalyst MCM-41 loads are sequentially added after dissolving
Sour (0.017g) continues to stir, while temperature is reduced to 25 DEG C, after the reaction was continued for 24 hours, after the completion of TLC detection reactions, under reduced pressure
Solvent methanol and ethyl alcohol are removed, residue is filtered, extraction and column chromatography, obtains target fire retardant Ia, yield 57.01%.
Yield：39.22%.
The new flame retardant of the structure provided by the invention containing melamine is as epoxy resin, polyurethane flame-proof additive
Using as follows：Batten is made according to insulating laminated sheet combustibility testing standard, is carried out respectively with JF-3 types oxygen index measurer
Limit oxygen index (LOI) is tested, and FZ-5401 types Vertical combustion instrument carries out the test of UL94 vertical combustions performance, and measurement result is as follows
Shown in Tables 1 and 2.
Table 1：1 fire retardant of the embodiment of the present invention is to the flame retardant effect of polyurethane
Table 2：1 fire retardant of the embodiment of the present invention is to the flame retardant effect of epoxy resin
The new flame retardant thermostabilization of the structure containing melamine of the present invention is good, and fire-retardant rate is high.The new flame retardant is three
The important supplement of poly cyanamid based flame retardant, while have higher potentiality on epoxy resin, polyurethane cooperative flame retardant additive
With wide application value.The research of the fire retardant of the new structure containing melamine is necessary and very urgent.This hair
Bright patent provides the novel preparation method that a kind of manufacturing cost is low, easy to operate, selectivity is good and reaction efficiency is high.
Claims (10)
1. the fire retardant of a kind of structure containing melamine, which is characterized in that the reaction equation is：
Wherein, substituent R1、R2And R3For hydrogen, tertiary butyl, normal-butyl, the alkyl of cyclohexyl or chloride, bromine, methyl, methoxyl group,
Nitro, amino, hydroxyl substituted aryl or heteroaryl in any one, substituting group position, number and conjugate position be not solid
Determine or including more than fire retardant composite fire retardant as main component.
2. the fire retardant of the structure described in claim 1 containing melamine, which is characterized in that the reaction equation is：
3. the fire retardant of the structure described in claim 1 containing melamine, which is characterized in that the reaction equation is：
4. the fire retardant of the structure described in claim 1 containing melamine, which is characterized in that the reaction equation is：
5. synthesize the method for claim 1-4 any one of them melamine class compounds, which is characterized in that the method bag
Include following synthesis path：
It the described method comprises the following steps：
(1) under nitrogen protection, sequentially add compound 1 into reactor, compound 2, compound 3, compound 4, methanol with
The mixed solvent of isopropanol, being stirred 30 minutes at 45-60 DEG C makes its dissolving；
(2) copper complex, MIL-101 and the p-methyl benzenesulfonic acid that catalyst MCM-41 loads are sequentially added after dissolving continue to stir,
Temperature is reduced to 30-40 DEG C simultaneously, the reaction was continued 20-28h, after the completion of TLC detection reactions, removes solvent methanol and second under reduced pressure
Alcohol, residue is filtered, extraction and column chromatography, obtains target compound I, completes the preparation of melamine based flame retardant.
6. according to the method described in claim 2, it is characterized in that：Compound 1 in the step (1), compound 2, compound
3, the molar ratio of compound 4 is 0.1-2：2-5：1-4：1-4.
7. according to the method described in claim 2, it is characterized in that：Compound 1 in the step (1), catalyst MCM-41 are born
The copper complex of load, the mass ratio that feeds intake of MIL-101 and p-methyl benzenesulfonic acid is 1：0.05-1：0.05-1：0.05-1.
8. according to the method described in claim 2, it is characterized in that：The solution temperature of the step (1) is 50 DEG C；Step (2)
Reaction temperature be 40 DEG C.
9. according to the method described in claim 2, it is characterized in that：Step (1) solvent is the mixing of methanol and isopropanol
Solvent, and the volume ratio of methanol and isopropanol is 2：1.
10. the fire retardant of the structure containing melamine being prepared described in any one described in claim 5-9 is in epoxy
Application on resin, polyurethane cooperative flame retardant additive.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422881A (en) * | 2001-12-05 | 2003-06-11 | 长春人造树脂厂股份有限公司 | Flame-retarding nitrogenous epoxy resin and its composition |
| EP1882475A1 (en) * | 2006-07-26 | 2008-01-30 | Novartis AG | Method of treating disorders mediated by the fibroblast growth factor receptor |
| CN101429438A (en) * | 2008-12-23 | 2009-05-13 | 山东天一化学有限公司 | Phosphor-nitrogen expansion type combustion inhibitor and method of producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422881A (en) * | 2001-12-05 | 2003-06-11 | 长春人造树脂厂股份有限公司 | Flame-retarding nitrogenous epoxy resin and its composition |
| EP1882475A1 (en) * | 2006-07-26 | 2008-01-30 | Novartis AG | Method of treating disorders mediated by the fibroblast growth factor receptor |
| CN101429438A (en) * | 2008-12-23 | 2009-05-13 | 山东天一化学有限公司 | Phosphor-nitrogen expansion type combustion inhibitor and method of producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110423225A (en) * | 2019-06-28 | 2019-11-08 | 中北大学 | A kind of preparation method and applications containing melamine compound |
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